Mercuri-acetylide compounds and method of preparing same



Patented Feb. 13, 1945 MERCURI-ACETYLIDE COM1OUNDS AND METHOD OF PREPARING SAME Morris H. Daskais, Chicago, 111., assignor to Research Corporation, a corporation of New York No Drawing. Original application October 9,

1939, Serial No. 298,635. Divided and this application November 23, 1942, Serial No. 466,663

8 Claims. v (Cl. 260-313) The present invention relates to a new series of mercuri-acetylide compounds and to methods of producing the same. It will be fully under.- stood from the following description, illustrated by specific examples of compounds of the present invention and their preparation.

' This application is a division of my copending application Serial No. 298,635, filed October 9. 1939.

Various mercuri-acetylide derivatives have been prepared by methods hitherto described; for example, various bis-alk'oxy-alkyl-mercuri-acetylides have been prepared by the methodof Nieuwland et ,al. (J. Am. Chem. Soc., vol. 55 (1933) Pp. 2465, 3728), of which bis-p-methoxyethyl-mercuri-acetylide may be regarded as typical. In general, such compounds have little or no soluthe reactants be completely dissolved, although these conditions are not essential. The solvent hydrocarbon group which is apparently bonded to bility in water and inw'eak alkaline aqueous solutions and aresoluble only with difficulty in such organic solvents as methanol, ethanol and acetone. Hence the use of such compounds is restricted, particularly where fungicidal and germicidal effects are desired.

in which R1 representsan alkyl group and R: a hydrocarbon radicalof the class consisting of the aliphatic and alicyclic groups. Such compounds may be prepared by the method of Nieuwland et 81., above referred to. I react uponsuch a compound with an organic nitrogen compound gen- 'erally which has an amido or imido radical'contaming a replaceable'labile or acidic hydrogen atom, thereby replacing the. R1O-- or alkoxy roup of the mercuri-acetylide compound. Orsanic nitrogen compounds having the characteristics above set forth which I have employed in carrying out my reaction include the amides and imides of carboxylic and sulfonic acids, and also various pyrroles and pyrrole derivatives, morpholine and the like. For example, I have used acetamide, propionamide, urea, benzamide, salicylamide, phthalimide, succinimide, 5,5-diethylbarbituric acid,benzene sulfonamide, amino-benmn'e sulfonamide, paratoluene sulfonamide, mor-- pholine. carbazole, and .pyrrole.

The reaction is preferably conducted in the' Presence of an organic solvent in which the reactants are partially or completely soluble. It is preferred that the solvent selected has a boiling point below the meltin: point of the mercuria nitrogen atom of an organic nitrogen compound and preferably to'a nitrogen atom or an amido or imido group in the organic nitrogen compound. This structure is indicated by the fact that, when reacted uponwith sodium stannite, the compounus produced yield metallic mercury very slowly as contrasted with compounds having a mercurynitrogen linkage, which, with the samereagent yield metallic mercury quickly.

The compounds produced in accordance with' my inventionhave the probable general formula.

wherein lA)- s an organic nitrogen-containing group of the class consisting of substituted amido and. substituted imido groups and R is a hydrocarare characterized by their solubility in water, di-

lute aqueous alkaline solutions or both, as well as various organic solvents.

The compounds of my invention are of particular value as germiciues and fungicides, for example, in the treatment of wood, ,m cut or uncut form to prevent 'iunglls diseases such as blue stain" on lumber, and in the treatment of seed to disinfect and immunize the same against infection. These compounds are substantially odoracetylide compound used in the reaction and that less and, for all practical purposes, are non-corrosive to iron, hence lending themselves for use in iron machinery and the like. An outstanding advantage of the compounds in accordance with my invention is the fact that they" are nonvesicant and do not irritate or cause blistering of the skin, thereby enabling them to be handled without fear of injuriously affecting the operator or user. I have found that seeds can tolerate large amounts of the compounds of my invention and the treated seed is stable and undergoes substantially no deterioration in storage.

The following examples illustrate methods of preparing soluble organic mercury compounds in accordance with my invention. It is, of course,

to be understood that my invention is not to be construed as limited to the proportions and demercury slowly on the addition of sodium stantails of-the methods therein set forth, since varnite.

ious modifications thereof will be apparent and If desired, the compounds bis-beta-ethoxyare intended to be included within the scope of ethyl-mercuri-acetyiene, bis-delta-propyioxybumy invention as defined by the app nded claims. a tyl mercuri acetylene, bis-cyclohexyloxyethyla ege pl the term indicates parts m ercuri-acetylene and the like may be reacted Example 1 ucts similar to that obtained in accordance with 20 parts of bis-beta-methoxyethyl mercurithis e acetylene and 13 parts of phthalimid are dis- Iclaimz' solved in about 300 parts of isopropyl alcohol. 1. The compound, bis-beta-phthalimido-N- The solution is refluxed for about two hours, at ethyl-mercuri-acetylene. which time the reaction is completed, and the 2. The compound having the formula.

" Bio-co co-oni N-CHr-QH:CHr-HgCECHgCH:-CHr-CHr-N Rio-co 00- H, solvent is removed as by vacuum distillation. The i 3. The method of preparing soluble organic reaction product, apparently the compound bismercury compounds which comprises reacting a beta phthalimido-N-ethyl-mercuri-acetylene, is mercuri-acetylide compound having the general dried in vacuo. The compound is soluble in warm formula aqueous sodium carbonate and in boiling water.

It sinters at 142 C. and melts completely at 1-- R2 C CH -Rz -R1 166 C,

with succinimide as in Example 2 to obtain prod- In tests conducted by me I have found that wherein R1 represents an alkyl group and a this compound will km the stain" fungi hydrocarbon radicalof the class consisting of the cemtostomeua pill-fem and Grapmum Tigidum; in aliphatic and ahcychc radicals, with phthalimide.

.a nutrientagar medium in a concentration less The methd 0f Preparing Soluble organic than 1 part per million. This reaction product which 00111914895 reacting is also toxic to the wood rotters, Fomes annosus mercurbacetynde having the general and Lenzites tmbea in concentrations of one-half formula I part per million.

400 times its weight in water to form an impreg- The compound bis-'beta-phthalimido-N-ethyl- B mercuri-acetylene is effective as a blue stain wherein R re r sents an W and R a previelrtat iyveko for tifiglnple, a g2; hydrocarbdn r ad ical of th a a las s c nsisting of am 0 o of compoun and 0 to 90% of sodium carbonate is dissolved in about mi zf i ahcychc radicals with succm t 5. The method of preparing soluble organic hating solution which is especially suitable for 40 this pumose. The wood either green or pap mercury compounds which comprises reacting a tially dried, is dipped into this impregnating solugifig compound having the general tion and'the wood is thereby protected against.

theaction ofstain and rot fungi. I .o c o B,

This phthalimido compound i also especially suitable as a dry seed disinfectant. For this purwherein R1 represents an alkyl group and R8 a pose, it is mixed with the usual inert diluents hydrocarbon radical of the class consisting of the, Such a for P Starch, kleselguhr, aliphatic and alicyclic radicals, with an organic Clay 1' p m, h or Without a Wetting 60 compound containing a diacyl bonded nitrogen agent- Thus, e, a nif and i atom leaving only one replaceable hydrogen mate mixture of about 5 parts by weight of bisto beta-phthalamido-N-ethyl-mercuri-acetylene in 6. The method of preparing soluble organic about 95 parts of talc provides a highly effective mercury compounds which comprises reacting a immunizer against seed-home fungus diseases mercuri-acetylide compound having the general when used in the ratio of about one-half to about formula 2 ounces per bushel of seed. v

10v parts of bis-gamma-methoxypropylmerwherein R1 represents an alkyl group and R: a curi-acetylene and 4 parts of succinimide are hydrocarbon radical of the class consisting of the dissolved in about 200 parts of dioxan. The solualiphatic and alicyclic radicals, with an amide tion is refluxed for about two hours at which, having the general formula R2 NH wherein 82 time the reaction is complete, and the solvent. is an acyl radical and wherein each carbonyl is removed as by vacuum distillation. The reacroup of the acyl adi al is ar on bonded to the tion product, which appears to have the formula 05 nitrogen atom.

aqueous sodium. carbonate, acetone, methanol of the general formula and is an effective germicide and fungicide. The compoundldoes not deposit mercuric oxide when (A) R Hg c=C -Hg R (A) treated with caustic soda and yields metallic 76. wherein A) is an organic radical containing a in c0 7 00- n, I

is dried in vacuo. The product is soluble in water, I. A symmetrical organic mercury c mpound diacyl imidonitroscn atom and a u a hydrocarhon radical of the class consisting of the aliphatic (m-n-m-cnc-Hc-n-m wherein (A) is a dicarboxylicacid amide radical and R is ahydrocarbonradical of the class consisting of the aliphatic and alicyclic hydrocarbon radicals, the said nitroaen atom of radical (A) bein bonded tca carbon atom or the hydrocarbon radical R.

MOB-RIB H. DASKAIS. 

